ISSN 0040-5795, Theoretical Foundations of Chemical Engineering, 2007, Vol. 41, No. 5, pp. 572–576. © Pleiades Publishing, Ltd.

, 2007.
Original Russian Text © D.F. Kondakov, V.P. Danilov, 2007, published in Khimicheskaya Tekhnologiya, 2007, Vol. 8, No. 1, pp. 2–6.

INORGANIC TECHNOLOGY

Manufacturing of Magnesium Hydroxide from Natural

Magnesium Chloride Sources
D. F. Kondakov and V. P. Danilov
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow, 119991
Russia
e-mail: danilov@igic.ras.ru
Received September 28, 2006

Abstract—Various processes for manufacturing magnesium hydroxide have been considered and tested in
order to decide whether they can be employed to the full-scale production of this product from natural sources
(bischofite and magnesium chloride brines). The process for the synthesis of magnesium hydroxide from mag-
nesium chloride using sodium hydroxide has been improved.

DOI: 10.1134/S0040579507050193

INTRODUCTION and Eriochrome Black indicator [2]; carbonates were

A process for preparing magnesium hydroxide from
magnesium chloride is needed for the following rea-
sons: Mg(OH)2 is a valuable and widely used chemical
product [1]; its natural deposits are rare (e.g., a brucite
deposit on the Far East on the Russian Federation), as
distinct from sodium magnesium, whose large deposits
exist on the territory of the Russian Federation and the
ancient Soviet Union (Volgograd bischofite, magne-
sium chloride brines in Kara-Bogaz-Gol, and others).
The following processes are now known for prepar-
ing magnesium hydroxide [1]: the thermal decomposi-
tion of salts to oxide and subsequent hydration of the
latter; direct precipitation of magnesium hydroxide
with alkali from solutions of magnesium salts; precipi-
tation of basic magnesium carbonates from salt solu-
tions, followed by their thermal decomposition to mag-
nesium oxide and the hydration of the latter; and mag-
nesium hydroxide precipitation from solution with lime
milk.
Our goal in this work was to experimentally study
the utility of the specified processes for preparing mag-
nesium hydroxide from bischofite (MgCl2 · 6H2O) and
magnesium chloride brines.
Inasmuch as the precipitation of magnesium
hydroxide from solution with lime milk is used in the
processing of dilute magnesium-containing solutions
(such as seawater, native brines, and some others) [1],
this process is not considered in this work.
EXPERIMENTAL
In this work, magnesium in samples was determined
chelatometrically by a standard procedure using EDTA
determined as carbon dioxide by chromatographing
the calcination products at 1000°C on Carlo Erba Ele-
mental Analyzer EA1108. Thermogravimetric experi-
ments were carried out on a Q-1500D Paulik-Paulik-
Erdey thermal analyzer. The phase composition was
monitored by X-ray powder diffraction on a DRON-1
diffractometer using CuKα radiation.
The starting reagents were sodium hydroxide and
sodium carbonate of reagent grade, distilled water, and
crystalline magnesium chloride flakes from Bischofite-
Avangard. The formula of the latter was MgCl2 · 6H2O;
the specified composition, in wt %: MgCl2, 46–47;
CaCl2, 0.4; NaCl, 0.7; KCl, 0.3; Br, 0.6; and sulfates, 0.06.
Chemical analysis determined 46.8% MgCl2 in the
starting reagent, which corresponds to 99.94% MgCl2 ·
6H2O. The DTA weight loss during the heating of the
reagent was 80.12% (Fig. 1), which also matches the
calculated concentration of 99.94% MgCl2 · 6H2O in
the reagent.
RESULTS AND DISCUSSION
Thermal Decomposition of Magnesium Chloride
When magnesium chloride hexahydrate is heated, it
first melts in its own water of crystallization; then, basic
magnesium chloride is formed as a result of hydrolysis
[1]; during subsequent heating, the latter decomposes
to magnesium chloride:
MgCl 2 ⋅ 6H 2 O MgCl 2 + 6H 2 O
Mg ( OH ) m Cl 2 – m + mHCl (1)
MgO + ( 2 – m )HCl.

572
 MANUFACTURING OF MAGNESIUM HYDROXIDE FROM NATURAL
The DTA traces for a commercial magnesium chlo-
ride hexahydrate sample (Fig. 1) display a series of
endotherms, which signify a multistage process. The
match between the observed weight loss and the value
calculated from the equation of reaction (1) (the differ-
ence is 0.06%) validates the high quality of the starting
magnesium chloride, on one hand, and the completion
of reaction (1), on the other.
This process for manufacturing magnesium hydrox-
ide from magnesium chloride hexahydrate has the fol-
lowing strength: additional reactants are not required,
except for water added during the hydration of magne-
sium oxide to hydroxide; as a result, the embodiment of
this process requires simpler equipment compared to
the other processes considered here. In particular, a pre-
cipitation reactor is not required. Another strength of
this process is the feasibility of obtaining one more
product, namely, hydrogen chloride. However, the
extremely high corrosiveness of hydrogen chloride at
elevated temperatures, a significant volume of hydro-
gen chloride (1250 kg HCl per ton of final Mg(OH)2),
and the necessity for cooling and absorbing it hamper
the embodiment of the process. In addition, the process
is extremely hazardous for operators.
Precipitation of Magnesium Hydroxide from Sodium
Hydroxide Solution
The reaction of magnesium chloride with a sodium
hydroxide solution by the equation
MgCl 2 + 2NaOH Mg ( OH ) 2 + 2NaCl (2)
produces a jelly, slowly filtration magnesium hydroxide
precipitate, which hampers filtration and washing
stages.
Therefore, we studied whether changing concentra-
tions of the reacting MgCl2 and NaOH solutions can
help improve the filtration properties of magnesium
hydroxide precipitates. For this purpose, two versions
of the reaction between magnesium chloride and
sodium hydroxide were studied: the reaction between
solid MgCl2 · 6H2O and solid NaOH without water
added and the reaction between dilute solutions of the
reagents. In both cases, the filtration rate of the result-
ing magnesium hydroxide precipitate was extremely
low. Likely, the reagent concentrations in the range
specified do not noticeably influence the particle size or
properties of magnesium hydroxide.
The duration of reaction (2) was also varied via
varying the rate of dispensing of aqueous alkali to mag-
nesium chloride solution. Within periods of 20 s to 12
min, the reaction time did not noticeably influence the
filtration and washing rates of magnesium hydroxide
precipitates.
Freezing can sometimes help agglomerate jelly pre-
cipitates [3]: particles coarsen during freezing due to
their compression by internal pressure, which is created
by an increase in the volume upon the phase transition
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
573
TG
DTA
712
977
536
132
314
–59.45%
314
536
259 –80.12%
220 820
Fig. 1. Thermoanalytical curves for the decomposition of
magnesium chloride hexahydrate.
from liquid water to ice. Our studies showed that the
freezing of a wet magnesium hydroxide precipitate via
dipping it into liquid nitrogen did not coarsen gel parti-
cles, nor it influenced the filtration rate.
We also studied whether magnesium hydroxide gel
particles can coarsen during heat treatment at 100–
700°C. Mixtures to be heat-treated consisted of the
products of the reaction between solid NaOH and solid
MgCl2 · 6H2O, which contained a jelly magnesium
hydroxide precipitate, sodium chloride, and a minor
amount of a saturated sodium chloride solution. The
experiment was intended to exclude the filtration and
washing of jelly magnesium hydroxide from the flow-
sheet.
Heat treatment was carried out in a muffle furnace;
the temperature was monitored with a thermocouple. To
interpret the processes that occurred during heat treat-
ment, heating traces were recorded (Figs. 2, 3). The
heating traces show that water first vaporized. Then, at
322–439°C, magnesium hydroxide was dehydrated; the
weight loss fully correlated with the reaction
Mg ( OH ) 2 MgO + H 2 O. (3)
The endotherm at 814°C was due to the melting of
sodium chloride.
After heat treatment was over, in order to separate
the sodium chloride from the product magnesium oxide
and to convert the latter to hydroxide, water was added
to the mixture of magnesium oxide and sodium chlo-
ride (1.80 g MgO + 3.63 g NaCl) to bring the volume to
20 ml; sodium chloride dissolved, while magnesium
oxide converted to hydroxide. Part of the MgO had not
enough time to convert to Mg(OH)2 at this stage; there-
fore, a mixture of magnesium oxide and magnesium
hydroxide entered the filtration stage. The precipitate
Vol. 41 No. 5 2007
574 KONDAKOV, DANILOV

was filtered from an NaCl solution and washed with
water. Filtration was carried out in vacuo on a Buchner
funnel using two White Band filters 55 mm in diameter.
The volume of the MgO + Mg(OH)2 + NaCl slurry was
20 ml; the wash-water volume was 20 ml. The washed,
wet precipitate was allowed to stand for ~1 h at 20°C to
fully convert magnesium oxide to hydroxide; the latter
was then dried.
The flowsheet for magnesium hydroxide prepara-
tion from magnesium chloride is shown below.

Precipitation Heat treatment NaCl Filtration Complete Drying

of magnesium of an Mg(OH)2 + dissolution and washing MgO of Mg(OH)2
hydroxide + NaCl + H2O and MgO of an Mg(OH)2 + hydration
frommagnesium mixture hydration + MgO mixture
chloride and from NaCl
sodium hydroxide solution

The results of the set of experiments are listed in the
table.
The table makes it clear that, after the precipitate
was heated to 650–700°C, its filtration and washing
rates became several times the filtration rate of magne-
sium hydroxide prepared at 20°C. Calcination at 700°C
for 20 min gave the best results. The filtered and water-
washed MgO + Mg(OH)2 mixture fully converted to
magnesium hydroxide after the wet precipitate was
allowed to stand at 100°C for 20–30 min.
Although the flowsheet seems illogical (first, mag-
nesium hydroxide is dehydrated, then the dehydration
product (magnesium oxide) is converted back to
hydroxide), this process can be positioned as techno-
logically acceptable because of the significant effi-
ciency of filtration and the noticeable improvement of
the washing of magnesium hydroxide from sodium
chloride.
Magnesium Precipitation from Solution with Sodium
Carbonate
It is known that the reaction of sodium carbonate
with water-soluble magnesium salts yields a mixture of
basic magnesium carbonates [1]:
Na 2 CO 3 + MgCl 2
(4)
Mg ( OH ) 2 – x ( CO 3 ) 0.5 – x + NaCl.

The mixture produced by the reaction of solutions of

TG magnesium chloride and sodium carbonate was care-
DTA fully washed from sodium chloride and dried to con-

TG
322

DTA 982
439

346 401

174

408 792 819

Fig. 2. Thermoanalytical curves for the decomposition of a Fig. 3. Thermal curves for the decomposition of a mixture
mixture of Mg(OH)2, NaCl, and water. of Mg(OH)2 and NaCl.

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 41 No. 5 2007

 MANUFACTURING OF MAGNESIUM HYDROXIDE FROM NATURAL 575

Results of experiments intended to prepare magnesium hydroxide via precipitation with sodium hydroxide followed by heat
treatment and hydration

Synthesis Calcining time, Degree of washing Degree of hydration

Filtering time, s Washing time, s
temperature, °C min MgO from NaCl, % at 20°C for 10 min, %

<–50* – 590 1293 – –

20** – 471 1323 85.11 100
500 20 250 767 88.98 100
600 20 202 589 91.63 88.10
650 20 174 530 93.91 82.84
700 20 50 56 97.27 37.73
700 1 67 85 97.56 44.32
700 90 65 102 96.94 22.24
750 1 – – 99.37 5.78
750 1 – – 95.91 89.65**
*Freezing temperature in liquid nitrogen.
**Magnesium hydroxide synthesis temperature.
***Hydration at 100°C for 80 min.

stant weight at 120°C, and its composition was deter-
mined.
X-ray powder diffraction showed a phase with the
parameters similar to those of basic magnesium car-
bonates and did not show Mg(OH)2 and MgCO3
phases.
From chemical, X-ray powder diffraction, and dif-
ferential thermal analyses, we can infer that the precip-
itate was a mixture of basic magnesium carbonates with
the bulk formula Mg7.45(CO3)6.45(OH) · 5.68H2O,
which contained a minor water-insoluble residue
(1.25%).
This precipitate of basic magnesium carbonates was
rapidly filtered and washed at room temperature; the fil-
tration and washing rates were virtually unaffected by
the concentration of the starting reagent solutions.
Under the conditions comparable with those employed
to precipitate magnesium hydroxide from solution with
sodium hydroxide, the slurry-filtration time and the
precipitate-washing time were 60 and 120 s, respec-
tively. The concentrations of the starting sodium car-
bonate and magnesium chloride solutions should be
such that reaction (4) produce an unsaturated sodium
chloride solution; this would ease precipitate washing.
The filtered and washed precipitate after drying was a
free-flowing fine powder.
From DTA data (Fig. 4), the decomposition of basic
magnesium carbonates ended at 520°C. In this connec-
tion, basic magnesium carbonates were calcined at
550°C for 1 h in order to provide their complete decom-
position to MgO. X-ray powder diffraction showed that
pure magnesium oxide was produced under these con-
ditions. The difference between the DTA weight loss on
calcining and the calculated value was 0.42%. Thus, the
temperature chosen (550°C) provided the complete
decomposition of basic carbonates and the production
of pure magnesium oxide.
The following stage—conversion of magnesium
oxide to hydroxide—met no difficulties: magnesium
oxide that formed at ~550°C was easily converted to
hydroxide when brought in contact with water (table).
After magnesium oxide prepared at 550°C was moist-
ened and allowed to stand for 50 min at room tempera-
ture, the magnesium hydroxide yield was 100%; after
boiling a magnesium oxide suspension with water for
30 min, the yield was also 100%.
The flowsheet of magnesium hydroxide preparation
from magnesium chloride via the precipitation and
thermal decomposition of basic magnesium carbonates
is shown below.

Precipitation of basic Filtration of basic Thermal Hydration Drying

magnesium carbonates magnesium decomposition of magnesium of Mg(OH)2
from magnesium carbonates of basic oxide
chloride using and washing magnesium
sodium carbonate off NaCl carbonates

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 41 No. 5 2007

576 KONDAKOV, DANILOV

TG this process, magnesium hydroxide was precipitated

DTA
304
514
–56.42%
520
Fig. 4. Thermoanalytical curves for the decomposition of a
mixture of basic magnesium carbonates.
CONCLUSIONS
Various processes for manufacturing magnesium
hydroxide have been considered and tested in order to
decide whether they can be employed in the full-scale
production of this product from natural sources (bis-
chofite and magnesium chloride brines).
A process has been proposed for the synthesis of
magnesium hydroxide from magnesium chloride. In
with aqueous alkali, the product being obtained as a
precipitate with good filtration properties.
A process for preparing magnesium hydroxide from
magnesium chloride, based on the precipitation of basic
magnesium carbonates, their thermal decomposition,
and the hydration of the resulting magnesium oxide,
has been tested.
Parameter data have been obtained for both pro-
–1.5% cesses. These data were necessary for performance cal-
culations, choosing equipment, and experimental
1000
design for pilot studies.
REFERENCES
1. Pozin, M.E., Tekhnologiya mineral’nykh solei (udobre-
nii, pestitsidov, promyshlennykh solei, okislov i kislot)
(Technology of Mineral Salts: Fertilizers, Pesticides,
Industrial Salts, Oxides, and Acids), Leningrad:
Khimiya, 1974, part 1.
2. Unifitsirovannye metody analiza vod (General Water
Analyses), Moscow: Khimiya, 1973.
3. Khimicheskaya entsiklopediya (Encyclopedia of Chem-
istry), Moscow: Sovetskaya Entsiklopediya, 1990,
vol. 2.

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 41 No. 5 2007